Synthetic polymers having hydrogen bonding capability and containing polysiloxane moieties

ABSTRACT

Synthetic polymers having hydrogen bonding capability and one or more polysiloxane moieties are capable of providing two distinct properties to paper products, such as tissues, which properties heretofore have been imparted through the use of at least two different molecules. The backbone of these synthetic polymers is based on modified vinyl polymers, such as polyvinyl alcohol, polyacrylamides and polyacrylic acids.

BACKGROUND OF THE INVENTION

[0001] In the manufacture of paper products, such as facial tissue, bathtissue, paper towels, dinner napkins and the like, a wide variety ofproduct properties are imparted to the final product through the use ofchemical additives. Examples of such additives include softeners,debonders, wet strength agents, dry strength agents, sizing agents,opacifiers and the like. In many instances, more than one chemicaladditive is added to the product at some point in the manufacturingprocess. Unfortunately, there are instances where certain chemicaladditives may not be compatible with each other or may be detrimental tothe efficiency of the papermaking process, such as can be the case withthe effect of wet end chemicals on the downstream efficiency of crepingadhesives. Another limitation, which is associated with wet end chemicaladdition, is the limited availability of adequate bonding sites on thepapermaking fibers to which the chemicals can attach themselves. Undersuch circumstances, more than one chemical functionality competes forthe limited available bonding sites, oftentimes resulting in theinsufficient retention of one or both chemicals on the fibers. For morecomplex chemical systems it may desirable to have two or more functionaladditives retained in a specified ratio and/or spatial arrangementrelative to one another. Although the addition of chemicals in apre-determined ratio is easily achieved, retention of these chemicals ina predictable ratio is difficult using wet end chemical addition becauseof site competition and other influencing factors. Another limitation ofeither wet end or topical chemical addition is the inability topredictably locate functional chemical moieties in proximity to eachother on the fiber surface.

[0002] Therefore, there is a need for a means of applying more than onechemical functionality to a paper web that mitigates the limitationscreated by limited number of bonding sites and the unpredictable natureof chemical additive retention which limits the ability to retainfunctional groups in a specified ratio and/or spatial arrangement withrespect to one another.

SUMMARY OF THE INVENTION

[0003] In certain instances, two or more chemical functionalities can becombined into a single molecule, such that the combined molecule impartsat least two distinct product properties to the final paper product thatheretofore have been imparted through the use of two or more differentmolecules. More specifically, synthetic polymers, which are commonlyused in the paper industry as dry strength resins, wet strength resinsand retention aids, can be combined into a single molecule withpolysiloxanes, which are utilized in the paper industry as surfacemodifiers, release agents, antifoams, softeners, debonders, lubricantsand sizing agents. The resulting molecule is a synthetic polymer havinghydrogen bonding capability and polysiloxane moieties which can provideseveral potential benefits, depending on the specific combinationemployed, including: strength aids that impart softness; softeners thatdo not reduce strength; wet strength with improved wet/dry strengthratio; surface feel modifiers with reduced linting and sloughing;strength aids with controlled absorbency; retention aids that soften;and improved retention of polysiloxanes when added as a wet endadditive.

[0004] As used herein, “polysiloxanes” are macromolecules with apolymeric backbone of alternating silicon and oxygen atoms (i.e.siloxane bonds) of general structure —(SiR_(A)R_(B)O)_(n)— where R_(A)and R_(B) are any organofunctional group and may be the same ordifferent and n is an integer of 1 or greater. The “synthetic polymers”,as described herein, have a portion of their structure derived from thepolymerization of ethylenically unsaturated compounds which containpendant groups that can form hydrogen bonds, ionic bonds or covalentbonds with cellulose molecules in fibers, thereby increasing interfiberbonding. They include polyacrylamide, polyvinyl alcohol, polyacrylicacid, polymaleic anhydride, polymaleic acid, polyitaconic acid, cationicpolyacrylamides, anionic polyacrylamides, and the like. The syntheticpolymers as described herein may be water soluble, organic soluble orsoluble in mixtures of water and water miscible organic compounds.Preferably they are water-soluble or water dispersible but this is not anecessity of the invention. Also included within the definition are thesalts of the above mentioned acidic polymers. Substances which can becombined with the acidic portion of the polymers to make the saltsinclude the alkali metals such as K and Na usually added in form oftheir hydroxides, the aliphatic amines and alkanol amines, such saltsand methods of preparing such salts being well known to those skilled inthe art.

[0005] Depending upon the chemical and the desired impact on the papersheet, the synthetic polymers of this invention may be applied to thepaper web by any of the means known to those skilled in the art. Suchmeans include wet end addition, spray addition on the wet web, as acreping chemical sprayed on the Yankee dryer, or as a post treatmentaddition, including spraying, printing or coating.

[0006] Hence in one aspect, the invention resides in a synthetic polymerhaving hydrogen or covalent bonding capability and containing one ormore polysiloxane moieties, said synthetic polymer having the followingstructure (structure 1):

[0007] where:

[0008] a, b>0;

[0009] c, d≧0 such that c+d>0;

[0010] w≧1;

[0011] Q₁=a monomer unit or a block or graft copolymer containing apendant group capable of forming hydrogen or covalent bonds withcellulose. Preferred pendant groups for hydrogen bonding are —CONH₂,—COOH, —COO⁻M⁺, —OH and mixtures of said groups. Preferred pendantgroups for covalent bonding are aldehydes and anhydrides. M⁺ can be anysuitable counter ion including Na⁺, K⁺, Ca⁺² and the like.

[0012] Q₂=a block or graft copolymer containing the siloxane bonds (—SiR_(A)R_(B)O—). The R_(A) and R_(B) functional groups attached to the Siatom can be alkyl or aliphatic hydrocarbons, linear or branched orcyclic, saturated or unsaturated, substituted or unsubstituted (e.g.,containing —OH, —(EtO)_(n), —(PO)_(n), —COO—, —O—, —CONH—, —CONH₂—,—CO—, . . . etc). Q₂ may take the form of —Z₁—Q₂—Z₁′— where Z₁, Z₁′ areany bridging radicals, the same or different, whose purpose is toprovide incorporation into the polymer backbone and Q₂ is as definedpreviously;

[0013] Q₃=a monomer unit or a block or graft copolymer containing acharge functionality. Such charge functionality is preferably cationicbut may be anionic or amphoteric; and

[0014] Q₄=a monomer unit or a block or graft copolymer containing ahydrophilic moiety, which is desirable for making the material into aform suitable for papermaking. Q₄ may take the form of —Z₂—Q₄—Z₂′— whereZ₂, Z₂′ are any bridging radicals, the same or different, whose purposeis to provide incorporation into the polymer backbone and Q₄ is asdefined previously. Q₄ may be incorporated to offset the increasedpolymer hydrophobicity caused by introduction of the polysiloxanemoieties. Examples of suitable Q₄ moieties are (but not limited to) thealiphatic polyether derivatives of the formula —[(CR₁R₂)_(x)O]_(y)—R₃,wherein R₁, R₂ is H or CH₃, x≧2, y≧1 and R₃ is any suitable terminalgroup including —CH₃, —H, —C₂H₅, —NH₂.

[0015] It should be appreciated that when the Q₃ or other charged moietyis present in the synthetic polymer, that a suitable counterion will benecessary. Such counterions may or may not be represented in theformulas. Where such counterions are not represented in the formula itshould be understood that such an ion will exist. The specificcounterion is not critical for the invention, such counterion is onlynecessary for providing charge balance. For cationically charged groupsthe most common anions are those of the halides and alkyl sulfates. Foranionically charged groups on the polymer the most common counter ionswill be those of the alkali and alkaline earth metals as well as ammoniaand amine derivatives.

[0016] More specifically, the invention resides in a synthetic polymerhaving the following structure (structure 2):

[0017] where:

[0018] w≧1;

[0019] R₁, R₁′, R₂, R₃=H, C₁₋₄ alkyl;

[0020] a, b>0;

[0021] c, d≧0 such that c+d>0;

[0022] Q₄=a monomer unit or a block or graft copolymer containing ahydrophilic moiety, which is desirable for making the material into aform suitable for papermaking. Q₄ may take the form of —Z₂—Q₄—Z₂′— whereZ₂, Z₂′ are any bridging radicals, the same or different, whose purposeis to provide incorporation into the polymer backbone and Q₄ is asdefined previously. Q₄ may be incorporated to offset the increasedpolymer hydrophobicity caused by introduction of the polysiloxanemoieties. Examples of suitable Q₄ moieties are (but is not limited to)the aliphatic polyether derivatives of the formula—[(CR₁R₂)_(x)O]_(y)—R₃, wherein R₁, R₂ is H or CH₃, x≧2, y≧1 and R₃ isany suitable terminal group including —CH₃, —H, —C₂H₅, —NH₂;

[0023] R₀=any group capable of forming hydrogen or covalent bonds withcellulose. Preferred are —CONH₂, —COOH, COO⁻M⁺, —OH, —CONHCHOHCHO andmixtures of said groups;

[0024] A₁=—H, —COOH;

[0025] R₄=Z—R₆ radical where:

[0026] Z=aryl, —CH₂—, —COO—, —CONR′—, —O—, —S—, —OSO₂O—, —CONHCO—,—CONHCHOHCHOO— or any other radical capable of bridging the R₆ group tothe vinyl backbone portion of the molecule. (R′=H, alkyl);

[0027] R₆=a block or graft copolymer containing siloxane bonds;

[0028] R₅=Z₃—R₁₀—W;

[0029] Z₃=aryl, —CH₂—, —COO—, —CONH—, —O—, —S—, —OSO₂O—, any radicalcapable of bridging the R₁₀ group to the vinyl backbone portion of themolecule;

[0030] R₁₀=any linear or branched, aliphatic or aromatic hydrocarbon of2 or more carbons, preferably —(CH₂CH₂)—, —C(CH₃)₂CH₂CH₂—; and

[0031] W=—N′R₁₁, R₁₂, R₁₃ where R₁₁, R₁₂, R₁₃ is a C₁₋₄ alkyl group.

[0032] —[CH₂CR₃R₅]_(c)— may also be the residue formed byco-polymerization with dimethyldiallyl ammonium chloride. In this casethe charge-containing residue —[CH₂CR₃R₅]_(c)— will be the form ofmonomers with repeat units of structure:

[0033] In another aspect, the invention resides in a paper sheet, suchas a tissue sheet, comprising a synthetic polymer having hydrogenbonding capability and containing an polysiloxane moiety, said polymerhaving the following structure:

[0034] where:

[0035] a, b>0;

[0036] c, d≧0;

[0037] w≧1;

[0038] Q₁=a monomer unit or a block or graft copolymer containing apendant group capable of forming hydrogen or covalent bonds withcellulose. Preferred pendant groups for hydrogen bonding are —CONH₂,—COOH, —COO⁻M⁺, —OH and mixtures of said groups. Preferred pendantgroups for covalent bonding are aldehydes and anhydrides. M⁺ can be anysuitable counter ion including Na⁺, K⁺, Ca⁺² and the like;

[0039] Q₂=a block or graft copolymer containing the siloxane bonds (—SiR_(A)R_(B)O—). The R_(A) and R_(B) functional groups attached to the Siatom can be alkyl or aliphatic hydrocarbons, linear or branched orcyclic, saturated or unsaturated, substituted or unsubstituted (e.g.,containing —OH, —(EtO)_(n), —(PO)_(n), —COO—, —O—, —CONH—, —CONH₂—,—CO—, . . . etc). Q₂ may take the form of —Z₁—Q₂—Z₁′— where Z₁, Z₁′ areany bridging radicals, the same or different, whose purpose is toprovide incorporation into the polymer backbone and Q₂ is as definedpreviously; p1 Q₃=a monomer unit or a block or graft copolymercontaining a charge functionality. Such charge functionality ispreferably cationic but may be anionic or amphoteric; and

[0040] Q₄=a monomer unit or a block or graft copolymer containing ahydrophilic moiety, which is desirable for making the material into aform suitable for papermaking. Q₄ may take the form of —Z₂—Q₄—Z₂′— whereZ₂, Z₂′ are any bridging radicals, the same or different, whose purposeis to provide incorporation into the polymer backbone and Q₄ is asdefined previously. Q₄ may be incorporated to offset the increasedpolymer hydrophobicity caused by introduction of the polysiloxanemoieties. Examples of suitable Q₄ moieties are (but is not limited to)the aliphatic polyether derivatives of the formula—[(CR₁R₂)_(x)O]_(y)—R₃, wherein R₁, R₂ is H or CH₃, x≧2, y≧1 and R₃ isany suitable terminal group including —CH₃, —H, —C₂H₅, —NH₂.

[0041] More specifically, the invention resides in a paper sheet, suchas a tissue sheet, comprising a synthetic polymer having hydrogenbonding capability and containing an polysiloxane moiety, said polymerhaving the following structure:

[0042] where:

[0043] w≧1;

[0044] R₁, R₁′, R₂, R₃=H, C₁₋₄ alkyl;

[0045] a, b>0;

[0046] c, d>=0;

[0047] Q₄=a monomer unit or a block or graft copolymer containing ahydrophilic moiety, which is desirable for making the material into aform suitable for papermaking. Q₄ may take the form of —Z₂—Q₄—Z₂′— whereZ₂, Z₂′ are any bridging radicals, the same or different, whose purposeis to provide incorporation into the polymer backbone and Q₄ is asdefined previously. Q₄ may be incorporated to offset the increasedpolymer hydrophobicity caused by introduction of the polysiloxanemoieties. Examples of suitable Q₄ moieties are (but is not limited to)the aliphatic polyether derivatives of the formula—[(CR₁R₂)_(x)O]_(y)—R₃, wherein R₁, R₂ is H or CH₃, x≧2, y≧1 and R₃ isany suitable terminal group including —CH₃, —H, —C₂H₅, —NH₂;

[0048] R₀=any group capable of forming hydrogen or covalent bonds withcellulose. Preferred are —CONH₂, —COOH, COO⁻M⁺, —OH, —CONHCHOHCHO, andanhydride including mixtures of said groups;

[0049] A₁=H, COOH;

[0050] R₄=Z—R₆ radical where:

[0051] Z=aryl, —CH₂—, —COO—, —CONR′—, —O—, —S—, —OSO₂O—, —CONHCO—,—CONHCHOHCHOO— or any radical capable of bridging the R₆ group to thevinyl backbone portion of the molecule. (R′=—H, alkyl);

[0052] R₀=a block or graft copolymer containing siloxane bonds;

[0053] R₅=Z₃—R₁₀—W;

[0054] Z₃=aryl, —CH₂, —COO—, —CONH—, —O—, —S—, —OSO₂O— or any radicalcapable of bridging the R₁₀ group to the vinyl backbone portion of themolecule;

[0055] R₁₀=any linear or branched, aliphatic or aromatic hydrocarbon of2 or more carbons, preferably —(CH₂CH₂)—, —C(CH₃)₂CH₂CH₂—; and

[0056] W=—N⁺R₁₁, R₁₂, R₁₃ where R₁₁, R₁₂, R₁₃ is a C₁₋₄ alkyl group.

[0057] —[CH₂CR₃R₅]_(c)— may also be the residue formed byco-polymerization with dimethyidiallyl ammonium chloride. In this casethe charge-containing residue —[CH₂CR₃R₅]_(c)— will be the form ofmonomers with repeat units of structure:

[0058] In another aspect, the invention resides in a method of making apaper sheet, such as a tissue sheet, comprising the steps of: (a)forming an aqueous suspension of papermaking fibers; (b) depositing theaqueous suspension of papermaking fibers onto a forming fabric to form aweb; and (c) dewatering and drying the web to form a paper sheet,wherein a synthetic polymeric additive is added to the aqueoussuspension of fibers or to the web, said polymeric additive having thefollowing structure:

[0059] where:

[0060] a, b>0;

[0061] c, d ≧0;

[0062] w≧1;

[0063] Q₁=a monomer unit or a block or graft copolymer containing apendant group capable of forming hydrogen or covalent bonds withcellulose. Preferred pendant groups for hydrogen bonding are —CONH₂,—COOH, —COO⁻⁺M, 13 OH and mixtures of said groups. Preferred pendantgroups for covalent bonding are aldehydes and anhydrides. M+ can be anysuitable counter ion including Na⁺, K⁺, Ca⁺² and the like;

[0064] Q₂=a block or graft copolymer containing the siloxane bonds (—SiR_(A)R_(B)O—). The R_(A) and R_(B) functional groups attached to the Siatom can be alkyl or aliphatic hydrocarbons, linear or branched orcyclic, saturated or unsaturated, substituted or unsubstituted (e.g.,containing —OH, —(EtO)_(n), —(PO)_(n), —COO—, —O—, —CONH—, —CONH₂—,—CO—, . . . etc). Q₂ may take the form of —Z₁—Q₂—Z₁′— where Z₁, Z₁′ areany bridging radicals, the same or different, whose purpose is toprovide incorporation into the polymer backbone and Q₂ is as definedpreviously;

[0065] Q₃=a monomer unit or a block or graft copolymer containing acharge functionality. Such charge functionality is preferably cationicbut may be anionic or amphoteric; and

[0066] Q₄=a monomer unit or a block or graft copolymer containing ahydrophilic moiety, which is desirable for making the material into aform suitable for papermaking. Q₄ may take the form of —Z₂—Q₄—Z₂′— whereZ₂, Z₂′ are any bridging radicals, the same or different, whose purposeis to provide incorporation into the polymer backbone and Q₄ is asdefined previously. Q₄ may be incorporated to offset the increasedpolymer hydrophobicity caused by introduction of the polysiloxanemoieties. Examples of suitable Q₄ moieties are (but is not limited to)the aliphatic polyether derivatives of the formula—[(CR₁R₂)_(x)O]_(y)—R₃, wherein R₁, R₂ is —H or —CH₃, x≧2, y≧1 and R₃ isany suitable terminal group including —CH₃, —H, —C₂H₅, —NH₂.

[0067] More specifically, the invention resides in a method of making apaper sheet, such as a tissue sheet, comprising the steps of: (a)forming an aqueous suspension of papermaking fibers; (b) depositing theaqueous suspension of papermaking fibers onto a forming fabric to form aweb; and (c) dewatering and drying the web to form a paper sheet,wherein a synthetic polymeric additive is added to the aqueoussuspension of fibers or to the web, said polymeric additive having thefollowing structure:

[0068] where:

[0069] w≧1;

[0070] R₁, R₁′, R₂, R₃=H, C₁₋₄ alkyl;

[0071] a, b>0;

[0072] c, d≧0;

[0073] Q₄=a monomer unit or a block or graft copolymer containing ahydrophilic moiety, which is desirable for making the material into aform suitable for papermaking. Q₄ may take the form of —Z₂—Q₄—Z₂′— whereZ₂, Z₂′ are any bridging radicals, the same or different, whose purposeis to provide incorporation into the polymer backbone and Q₄ is asdefined previously. Q₄ may be incorporated to offset the increasedpolymer hydrophobicity caused by introduction of the polysiloxanemoieties. Examples of suitable Q₄ moieties are (but is not limited to)the aliphatic polyether derivatives of the formula—[(CR₁R₂)_(x)O]_(y)—R₃, wherein R₁, R₂ is H or CH₃, x≧2, y≧1 and R₃ isany suitable terminal group including —CH₃, —H, —C₂H₅, —NH₂;

[0074] R₀=any group capable of forming hydrogen or covalent bonds withcellulose. Preferred are —CONH₂, COOH, COO⁻, —OH, CONHCHOHCHO, andanhydride including mixtures of said groups;

[0075] A₁=—H, —COOH;

[0076] R₄=Z—R₆—Y radical where:

[0077] Z=aryl, —CH₂—, —COO—, —CONR′—, —O—, —S—, —OSO₂O—, —CONHCO—,—CONHCHOHCHOO— or any radical capable of bridging the R₆ group to thevinyl backbone portion of the molecule. (R′=H, alkyl);

[0078] R₆=a block or graft copolymer containing siloxane bonds;

[0079] Y=H, —N⁺R₁₁, R₁₂, R₁₃, —NR₇R₈, where R₇, R₈, R₉ are same ordifferent and are H or C₁₋₃₀ linear or branched, saturated orunsaturated aliphatic hydrocarbons;

[0080] At least one of R₆, R₇, R₈, R₉ must be an aliphatic, linear orbranched, substituted or non-substituted, hydrocarbon of chain length 8or higher;

[0081] R₅=Z₃—R₁₀—W;

[0082] Z₃=aryl, —CH₂—, —COO—, —CONH—, —O—, —S—, —OSO₂O— or any radicalcapable of bridging the R₁₀ group to the vinyl backbone portion of themolecule;

[0083] R₁₀=any linear or branched, aliphatic or aromatic hydrocarbon of2 or more carbons, preferably —(CH₂CH₂)—, —C(CH₃)₂CH₂CH₂—; and

[0084] W=—N⁺R₁₁, R₁₂, R₁₃ where R₁₁, R₁₂, R₁₃ is a C₁₋₄ alkyl group.—[CH₂CR₃R₅]_(c)— may also be the residue formed by co-polymerizationwith dimethyldiallyl ammonium chloride. In this case thecharge-containing residue —[CH₂CR₃R₅]_(c)— will be the form of monomerswith repeat units of structure:

[0085] The amount of the synthetic polymeric additive added to thefibers or the tissue web can be from about 0.02 to about 4 weightpercent, on a dry fiber basis, more specifically from about 0.05 toabout 2 weight percent, and still more specifically from about 0.1 toabout 1 weight percent. The synthetic polymer can be added to the fibersor web at any point in the process, but it can be particularlyadvantageous to add the synthetic polymer to the fibers while the fibersare suspended in water.

[0086] Methods of making paper products which can benefit from thevarious aspects of this invention are well known to those skilled in thepapermaking art. Exemplary patents include U.S. Pat. No. 5,785,813issued Jul. 28, 1998 to Smith et al. entitled “Method of Treating aPapermaking Furnish For Making Soft Tissue”; U.S. Pat. No. 5,772,845issued Jun. 30, 1998 to Farrington, Jr. et al. entitled “Soft Tissue”;U.S. Pat. No. 5,746,887 issued May 5, 1998 to Wendt et al. entitled“Method of Making Soft Tissue Products”; and U.S. Pat. No. 5,591,306issued Jan. 7, 1997 to Kaun entitled “Method For Making Soft TissueUsing Cationic Silicones”, all of which are hereby incorporated byreference.

DETAILED DESCRIPTION OF THE INVENTION

[0087] To further describe the invention, examples of the synthesis ofsome of the various chemical species are given below.

[0088] Modified Vinyl Polymers

[0089] First with regard to the modified vinyl polymers, they can bemade via free radical polymerization of vinyl monomers of the form:

R₁R₂C═CR₃R₄

[0090] where R₁, R₂, R₃, R₄ may be H, halogen, alkyl, functional alkyl,aryl, functional aryl. For papermaking the polyacrylamides (R₄═—CONH₂),polyvinyl alcohols (R₄═—OH), and polyacrylates (R₄═—COOR′, R′═H, Me) arethe most widely used.

[0091] Of the modified vinyl polymers, polyacrylamides (PAMs) are usedas dry strength additives in addition to their widespread use asdrainage and retention aids. They are water-soluble polymers containingprimary amide groups that can form hydrogen bonds with cellulosemolecules in fibers thereby increasing interfiber bonding. They aresynthesized by the free radical polymerization of acrylamide as shown inReaction 1.

[0092] PAMs are nonionic materials and have very little attraction topapermaking fibers. Therefore it is necessary to incorporate chargedgroups into the polymer structure to make it useful for papermaking.Both anionic and cationic polyacrylamides are known in the art.

[0093] Anionic polyacrylamides can be produced by (1) copolymerizationof acrylamide with acrylic acid; and (2) hydrolysis of some of the amidegroups on the polyacrylamide chain. The resultant polymer will contain amixture of acrylamide and acrylic acid groups. Anionic polyacrylamideswere first produced in the 1950's via copolymerization of acrylamidewith acrylic acid. The acrylic acid groups introduce an ionizablecarboxyl group on the polymer backbone. Ionization of these carboxylgroups is highly pH dependent where above pH 7 essentially 100% of thecarboxyl groups are ionized. Since anionic polyacrylamides arenegatively charged they are not directly attracted to the like chargedcellulose fibers. A cationic substance such as alum must be used inconjunction with them to promote their retention.

[0094] To avoid the need for a cationic promoter, another approach is toincorporate cationic groups directly into the polymer backbone. Havingbeen commercially produced since the late 1960's these cationicallycharged polyacrylamides are the most common form of dry strength PAM's.Cationic polyacrylamides are produced by copolymerization of acrylamidewith cationic monomers or by modification of some of the amide groups. Atypical reaction is illustrated in Reaction 2 for co-polymerization withMethacryuloyloxyethyl trimethyl ammonium methosulfate (METAMS). Typicalcationic monomers include: (1) methacryuloyloxyethyl trimethyl ammoniummethosulfate; (2) dimethyldiallyl ammonium chloride (DMDAAC); (3)3-acryloamido-3-methyl butyl trimethyl ammonium chloride (AMBTAC); (4)trimethylamino methacrylate; and (5) vinyl benzyl trimethyl ammoniumchloride (VBTAC). Such materials have structures similar to that shownin Reaction 2 for METAMS copolymerized cationic PAM.

[0095] The incorporation of cationic groups through modification ofnon-ionic polyacrylamide is most often accomplished via the Mannichreaction as illustrated in Reaction 3. Generally cationicpolyacrylamides will contain from about 5 to about 70% mole percentcationic groups.

[0096] Generally dry strength PAMs are supplied as ready to use aqueoussolutions or as water-soluble powders which must be dissolved prior touse. They may be added to thin or thick stock at a point of good mixingfor best results. Addition rates of 0.1% to 0.5% of dry fiber typicallygive best results. High addition rates may cause overcationization ofthe furnish and reduce the effectiveness of other additives.

[0097] When used as dry strength additives usually around 10 mole % ofthe monomers will contain charged groups. Unlike the anionic PAM's,cationic PAM's are effectively charged across the entire pH range.Typical molecular weights for cationic PAM dry strength aids are in therange of 100,000 to 500,000. The molecular weight is important so as tobe low enough to not bridge between particles and cause flocculation,and yet high enough to retard migration of the polymer into the pores ofthe fibers. Such migration would cause a reduction in dry strengthactivity.

[0098] When used as retention aids a broader range of molecular weightsand charge densities may be employed. Key characteristics ofpolyacrylamide retention aids include the molecular weight, the type ofcharge, the charge density and the delivery form. For the averagemolecular weight, the range can be: low (1,000-100,000); medium(100,000-1,000,000); high (1,000,000-5,000,000); very high (>5,000,000).The charge type can be nonionic, cationic, anionic or amphoteric. Thecharge density can be: low (1-10%); medium (10-40%); high (40-80%); orvery high (80-100%). The delivery form can be either an emulsion, anaqueous solution or a dry solid.

[0099] High molecular weight/low charge density flocculants are usedmost often for retention of fine particles in high shear and turbulenceenvironments. Low molecular weight/high charge density products are usedfor their charge modifying capabilities and for retention in low shearenvironments.

[0100] Polysiloxanes

[0101] With regard to the polysiloxane component, polysiloxanes can bemade using a three-step synthesis: chlorosilane synthesis, chlorosilanehydrolysis, followed by polymerization and polycondensation.

[0102] Chlorosilane Synthesis

Si+RCl—SiR′₄

[0103] where:

[0104] R=H, methyl or ethyl group, and

[0105] R′₄=Cl, H, methyl or ethyl.

[0106] This reaction is exothermic with a yield as high as 90%. Acopper-based catalyst is usually used. The resulting variouschloroalkylsilanes can be separated by fractionation distillation. Ifdesired, silanes of other functionalities can be obtained via furtherreactions. For instance:

[0107] where

[0108] R=alkyl, aryl, or other organofunctional group.

[0109] R′=methyl, ethyl or acetoxy

[0110] Chlorosilane Hydrolysis

[0111] Dimethyldichlorosilanes undergo exothermic hydrolysis to yielddisilanols which further condense to produce a variety of linear and/orcyclic oligomers:

[0112] n=20-50; and

[0113] m≧3

[0114] The linear and cyclic oligomers from the above hydrolysis need tobe further polymerized or condensed to produce a silicone macromoleculeof sufficient length.

[0115] Cyclic Polymerization

[0116] The (R₂SiO)_(n) cyclic oligomers undergo ring opening andpolymerization to form long linear chains. Polymer chain length aredetermined by the presence(concentration) of the chain endblocker.

[0117] wherein

[0118] m≧1

[0119] n≧3

[0120] z≧1

[0121] Copolymerization in the presence of a catalyst (Me₄NOH) can becarried out in the following scheme:

R₃SiOSi R₃+x(R₂SiO)₄→R₃SiO(R₂SiO)_(n) Si R₃

[0122] where

[0123] R=alkyl, aryl, or other organofunctional group.

[0124] X≧1

[0125] n≧4

[0126] Linear Condensation

[0127] The linear silanol condenses to give long chain siloxanes.

[0128] where

[0129] R=alkyl, aryl, or other organofunctional group

[0130] Attached to the silicon atom are organic side chains includingalkyl, aliphatic hydrocarbons, phenyl or vinyl groups. By adjusting the—SiO— chain length, the side chain functionality and the crosslinkingbetween molecular chains, silicones form an almost infinite number ofhybrid polymers. In fact, the industry has created a plethora of novelsilicones to provide various end use properties such as chemicalcompatibility, solubility, water repellency, lubrication, foam control,releasing aid, cooling, sealing, adhesion, coating and substantivity.

[0131] Organoreactive polysiloxanes and silanes are very useful inmaking hybrid polymers. The following are a few examples:

[0132] Copolymerization of Vinyl Silanes With an Organic Monomer

[0133] where

[0134] R₃ and R′ are chlorine, amine, methoxy, acetoxy, hydroxyl, vinyl,or silicone hydride functionalities

[0135] x≧1

[0136] y≧1

[0137] Grafting the Silicones to an Organic Polymer Backbone

[0138] where

[0139] R and R′ are chlorine, amine, methoxy, acetoxy, hydroxyl, vinyl,or silicone hydride functionalities

[0140] x≧1

[0141] Addition of Silicone Functionality

H—SiR₃+R′OH→R₃Si—OR′+H₂

[0142] where

[0143] R′=any organofunctional group

[0144] R=alkyl, aryl, or other organofunctional group.

[0145] Modified Vinyl Polymers Containing Polysiloxanes

[0146] There are several envisioned pathways in which synthetic polymerscontaining hydrogen bonding groups and polysiloxanes can be combinedonto a single molecule (structures 1 and 2) for purposes of thisinvention. These include, but are not limited to: (1) blockco-polymerization and/or grafting; (2) direct monomer incorporation; and(3) derivatization of functional groups on the polymer backbone, Each ofthese methods is described below. Since these materials maintain theirbonding and/or charge characteristics they would be expected to maintaintheir dry strength and or retention capabilities as well as provide formaterials with enhanced tactile properties due to introduction of thepolysiloxane moieties.

[0147] The molar and weight ratios of the various functional groups onthe polymer will largely depend on the specific application of thematerial and is not a critical aspect of the invention. However, withregard to structure 1, the portion of the synthetic polymer [Q₁] capableof forming hydrogen, covalent and ionic bonds can constitute from about10 to about 90 weight percent of the total polymer, more specificallyfrom about 20 to about 80 weight percent of the total polymer and stillmore specifically from about 30 to about 70 weight percent of the totalpolymer. The polysiloxane portion [Q₂] of the synthetic polymer canconstitute from about 10 to about 90 weight percent of the syntheticpolymer, more specifically from about 20 to about 80 weight percent ofthe synthetic polymer and still more specifically from about 30 to about70 weight percent of the synthetic polymer. The charge containingportion [Q₃] of the synthetic polymer can be comprised of monomer unitsconstituting from 0 to about 80 mole percent of the total monomer unitsin the synthetic polymer, more specifically from 0 to about 30 molepercent and still more specifically from about 5 to about 15 molepercent. The [Q₄] functionality will be comprised of monomer unitsconstituting from 0 to about 80 mole percent of the total monomer unitsin the synthetic polymer, more specifically from 0 to about 40 molepercent and still more specifically from 0 to about 20 mole percent.

[0148] Likewise the molecular weight of the synthetic polymers of thepresent invention will largely depend on the specific application of thematerial and is not overly critical to the invention. The weight averagemolecular weight range can be from about 1,000 to about 5,000,000, morespecifically from about 10,000 to about 2,000,000 and still morespecifically from about 20,000 to about 1,000,000. Where these polymersare added for dry strength it is important that the molecular weight ofthe polymer be low enough so as to not bridge between particles andcause flocculation, and yet high enough so as to retard migration of thepolymer into the pores of the fibers. These materials can have weightaverage molecular weights in the range of from about 5,000 to about1,000,000, more specifically from about 10,000 to about 1,000,000 andstill more specifically from about 20,000 to about 600,000.

[0149] Block Copolymerization and/or Grafting

[0150] In this aspect of the invention one or more of the [Q], elementsof the polymer exists as a block or graft copolymer on the vinylbackbone. These synthetic polymers are distinguished from those of thedirect monomer incorporation in that the polysiloxane portion of themolecule would be incorporated linearly within the polymer chain ratherthan in a pendant fashion. It should be appreciated that any of thesynthetic polymer elements or combination of the synthetic polymerelements Q₁, Q₂, Q₃, Q₄ could be incorporated via this approach. Notethat where a polyacrylamide is employed that these polymers maintainpendant amide functionality and are therefore capable of beingglyoxylated to form materials possessing temporary wet strength.

[0151] Direct Monomer Incorporation

[0152] Incorporation of the polysiloxane moieties can be accomplishedvia copolymerization with vinyl type monomers containing aliphaticgroups. Almost any vinyl type monomer containing a pendant polysiloxanemoiety can be co-polymerized with acrylamide or a similar vinyl monomercontaining a pendant hydrogen-bonding moiety to be incorporated into thepolymer backbone. Generically the synthesis can be described in Reaction4.

[0153] where:

[0154] R₁, R₁′, R₁″, R₁′″, R₁″″=H, C₁₋₄ alkyl;

[0155] a, b≧1;

[0156] c, d≧0;

[0157] w≧1;

[0158] r, s≧1;

[0159] t, u≧0;

[0160] a*w=r;

[0161] b*w=s;

[0162] c*w=t;

[0163] d*w 32 u;

[0164] R₀=any group capable of forming hydrogen or covalent bonds withcellulose. Preferred are —CONH₂, COOH, COO⁻, —OH, CONHCHOHCHO, andanhydride including mixtures of said groups;

[0165] A₁=H, COOH;

[0166] R₄=Z—R₆—Y radical where:

[0167] Z=Aryl, CH₂, COO—, CONH—, —O—, —S—, —OSO₂O—, —CONHCO—,CONHCHOHCHOO—, any radical capable of bridging the R₆ group to the vinylbackbone portion of the molecule;

[0168] Y=H, —N+R₇R₈R₉, —NR₇R₈, where R₇, R₈, R₉ are same or differentand are H or C₁₋₃₀ aliphatic hydrocarbons;

[0169] R₅=any aliphatic, linear or branched, saturated or unsaturated,substituted or non-substituted hydrocarbon;

[0170] R₁₄=a moiety necessary for making the material into a formsuitable for papermaking. R₁₄ may take the form of —Z₁—R₁₄ where Z₁ isany bridging radical whose purpose is to provide incorporation into thepolymer backbone and R₁₄ is as defined previously. R₁₄ may beincorporated to offset the increased polymer hydrophobicity caused byintroduction of the polysiloxane moieties. Examples of suitable R₁₄moieties are (but is not limited to) the aliphatic polyether derivativesof the formula —[(CR₁R₂)_(x)O]_(y)—R₁₅, wherein R₁, R₂ is H or CH₃, x≧2,y≧1 and R₁₅ is any suitable terminal group including —CH₃, —H, —C₂H₅,—NH₂, and the like; and

[0171] At least one of R₆, R₇, R₈, R₉ must be a C₈ or higher linear orbranched, saturated or unsaturated, substituted or non-substituted,aliphatic hydrocarbon.

[0172] More specifically, R₅=Z₃—R₁₀—W, where:

[0173] Z₃=Aryl, CH₂, COO—, CONH—, —O—, —S—, —OSO₂O—, any radical capableof bridging the R10 group to the vinyl backbone portion of the molecule;

[0174] R₁₀=any linear or branched, aliphatic or aromatic hydrocarbon of2 or more carbons, preferably —(CH₂CH₂)—, —C(CH₃)₂CH₂CH₂—; and

[0175] W=—N⁺R₁₁, R₁₂, R₁₃ where R₁₁, R₁₂, R₁₃ is a C₁₋₄ alkyl group.

[0176] R₅ can also be the residue formed by co-polymerization withdimethyldiallyl ammonium chloride. In this case the residue will be theform of monomers with repeat units of structure:

[0177] Polymers of the type shown in Reaction 4, which maintain pendantamide functionality, may further be modified to produce materialsexhibiting temporary wet strength as well as dry strength. Most notablythis may be accomplished through reaction with glyoxal. The generalreaction scheme is given in Reaction 5.

[0178] Incorporation of polysiloxanes can be accomplished via twoprimary routes: a) incorporation via copolymerization with vinyl typemonomers containing polysiloxanes or silane groups and b) reaction withfunctional groups attached to the modified polyvinyl backbone

[0179] Almost any vinyl type polymer can be co-polymerized withacrylamide to be incorporated into the polymer backbone. Generically thesynthesis can be described in Reaction 6.

[0180] where

[0181] R₀=any group capable of forming hydrogen bonds. Preferred but notlimited to are —CONH₂, OH, COOH, COO— including mixtures of said groups.

[0182] A₁=COOH, H

[0183] Z=Ar, CH₂, COO—, CONH—, —O—, —S—, —OSO₂O—, —CONHCO—,—CONHCHOHCHOO—, or any radical capable of bridging the R6 group to thevinyl backbone portion of the molecule.

[0184] R₄=Si(R′)₂—O—[Si(R″)₂—O]_(n)—Si(R′″)₃ where R′, R″, R′″ can bethe same or different, are selected from the following groups: H, OH,aryl, or alkyl or aliphatic hydrocarbon, C₁₋₄₀, linear or branched,saturated or unsaturated, substituted or non—substituted, with orwithout ethyoxylation and/or propoxylation.

[0185] R₅=Z₃—R₁₀—W

[0186] Z₃=Ar, CH₂, COO—, CONH—, —O—, —S—, —OSO₂O—, any radical capableof bridging the R₁₀ group to the vinyl backbone portion of the molecule.

[0187] R₁₀=any linear or branched, aliphatic or aromatic hydrocarbon of2 or more carbons, preferably —(CH₂CH₂)—, —C(CH₃)₂CH₂CH₂—W=—N+R₁₁, R₁₂,R₁₃ where R₁₁, R12, R₁₃ is a C₁₋₄ alkyl group.

[0188] CH₂=CR₃R₅ may also be dimethyldiallyl ammonium chloride. In thiscase the residue will be the form of monomers with repeat units ofstructure

[0189] A specific example is given as follows with synthesis shown inReaction 7. Vinyl siloxanes and polysiloxanes are known commerciallyavailable materials. They will have the general structure R₁R₂=R₃R₄where R₄ will contain the siloxane or polysiloxane moiety and R₁, R₂, R₃can be H, or various organic radicals including alkyl, alkoxy, etc. Theywould be expected to incorporate into any vinyl type polymer such as aPAM, PVA, etc. They would be incorporated directly into the polymerduring the polymerization process as described below. Description shownis specific for a polyacrylamide but is applicable to any vinyl typepolymer. As such the siloxanes are arranged on the polymer in a pendantfashion.

[0190] where

[0191] R₁, R₂=H, OH, alkyl, hydroxyalkyl, substituted or unsubstituted,linear or branched of chain length C₁₋₃₀, or—(CH₂)_(p)—O—(EtO)_(q)—(PO)_(r)—R₁′, where p≧0, q+r≧1

[0192] R₁′=H, Alkyl or hydroxyalkyl of C₁-C₃₀, substituted orunsubstituted, linear or branched;

[0193] R=H, OH, alkyl, hydroxyalkyl, C₁-C₃₀, or —(CH₂)_(n)—N(R′)₂ where

[0194] R′—H, alkyl, or hydroxyalkyl, substituted or unsubstituted,linear or branched, C₁-C₃₀

[0195] Note that since these polymers maintain pendant amidefunctionality they are capable of being glyoxylated to form materialspossessing temporary wet strength as shown in Reaction 8.

[0196] where

[0197] R₁, R₂=H, OH, alkyl, hydroxyalkyl, substituted or unsubstituted,linear or branched of chain length C₁₋₃₀, or—(CH₂)_(p)—O—(EtO)_(q)—(PO)_(r)—R₁′, where p>0, q+r>1

[0198] R₁′=H, Alkyl or hydroxyalkyl of C₁-C₃₀, substituted orunsubstituted, linear or branched;

[0199] R=H, OH, alkyl, hydroxyalkyl, C₁-C₃₀, or —(CH₂)_(n)—N(R′)₂ where

[0200] R′=H, alkyl, or hydroxyalkyl, substituted or unsubstituted,linear or branched, C₁-C₃₀

[0201] Derivitization of Functional groups on the Polymer Backbone

[0202] The second approach to synthesis of materials of structures 1 and2 is to modify the functional groups on the polymer backbone. The vinyltype polymers, including the modified polyacrylamides, polyacrylic acidand polyvinyl alcohol contain functional groups which may be furtherderivatized to produce materials of Reaction 4. The polymer functionalgroups which may be reacted upon include but are not limited to: amide,acyl, carboxyl, hydroxyl, cyano, and aldehyde (from glyoxylation orsimilar reaction). In general the starting polymer will be one of thatshown in the following structure 3:

[0203] R₁, R₁′, R₂, R₃=H, C₁₋₄ alkyl or hydroxyalkyl

[0204] a, b>=1

[0205] c>=0

Structure 3

[0206] where

[0207] R₁, R₁′, R₂, R₃=H, C₁₋₄ alkyl or hydroxyalkyl

[0208] a, b>=1

[0209] c>=0

[0210] R₀=any group capable of forming hydrogen bonds. Preferred are—CONH₂, COOH, OH, COO— including mixtures of said groups.

[0211] Z₄=—CONHCHOHCHO, —CONH₂, —COOH, —R—CN, —OH, —SH, —NH₂, —OH or anyother functional group capable of being reacted upon in a manner so asto incorporate a polysiloxane chain, (substituted or unsubstituted) intothe polymer.

[0212] R₅=Z₃—R₁₀—W

[0213] Z₂=Ar, CH₂, COO—, CONH—, —O—, —S—, —OSO₂O—, any radical capableof bridging the R₁₀ group to the vinyl backbone portion of the molecule.

[0214] R₁₀=any linear or branched, aliphatic or aromatic hydrocarbon of2 or more carbons, preferably —(CH₂CH₂)—, —C(CH₃)₂CH₂CH₂—W=—N⁺R₁₁, R₁₂,R₁₃ where R₁₁, R₁₂, R₁₃ is a C₁₋₄ alkyl group.

[0215] —[(CH₂CR₃R₅]_(c)— may also be the residue formed byco-polymerization with dimethyldiallyl ammonium chloride. In this casethe residue will be the form of monomers with repeat units of structure

[0216] Materials such as those shown in structure 3 are amenable toreaction with a large variety of reagents as a means of incorporatingpolysiloxanes into the polymer. A general derivatization scheme is shownin Reaction 9 with specific example given in Reaction 10.

[0217] where

[0218] X=a functional end group including —Cl, —H, —OH attached to thepolysiloxane capable of being reacted upon by a functional groupattached to the other polymer in a manner so as to incorporate thepolysiloxane moiety (substituted or unsubstituted, may contain variousdegrees of ethoxylation or propoxylation, may contain various functionallinkages such as ester, ether, amide, or amine) into the polymer;

[0219] Y=the polysiloxane moiety.

[0220] where

[0221] x, y=1-5000;

[0222] R, R′, R′″=CH₃;

[0223] R″=—(CH₂)_(a)—O—(C₂H₅O)_(m)—(C₃H₇O)_(n)—OH

[0224] where

[0225] a=2-6;

[0226] m=1-1000;

[0227] n=1-500.

[0228] If the end block functional groups are not reactive enough,silane coupling agents may be used to bridge the vinyl and the siloxanepolymers. An example is shown in Reaction 11. Silane coupling agentshave been used extensively by those skilled in the art tosemipermanently modify a substrate. In the skin care area, they havebeen used with materials to provide long lasting protective benefitssuch as: (1) nonocclusive water barriers to prevent over hydration ofthe skin; (2) humectants; (3) skin conditioners; (4) antimicrobials; and(5) sunscreening agents, etc. The same coupling agents can be bonded toa cellulosic substrate to attach, e.g., germicidal or lubricatingfunction to a tissue or towel or wipe.

[0229] where

[0230] x, y=1-5000;

[0231] R, R′, R′″=CH₃;

[0232] R″=—(CH₂)_(a)—O—(C₂H₅O)_(m)—(C₃H₇O)_(n)—OH

[0233] where:

[0234] a=2-6;

[0235] m=1-1000;

[0236] n=1-500.

[0237] It will be appreciated that the foregoing examples, given forpurposes of illustration, are not to be construed as limiting the scopeof this invention, which is defined by the following claims and allequivalents thereto.

We claim:
 1. A synthetic polymer containing one or more polysiloxanemoieties, said synthetic polymer having the following structure:

where: a, b>0; c, d≧0 such that c+d>0; w≧1; Q₁=a monomer unit or a blockor graft copolymer containing a pendant group capable of forminghydrogen or covalent bonds with cellulose; Q₂=a block or graft copolymercontaining siloxane bonds; Q₃=a monomer unit or a block or graftcopolymer containing a charge functionality; and Q₄=a monomer unit or ablock or graft copolymer containing a hydrophilic moiety, which isdesirable for making the material into a form suitable for papermaking.2. The polymer of claim 1 wherein the pendant group on Q₁ capable offorming hydrogen or covalent bonds is selected from the group consistingof —CONH₂, —COOH, —COO⁻M⁺, —OH, —CONHCHOHCHO or anhydrides and mixturesthereof, wherein M⁺ is a counter ion.
 3. The polymer of claim 1 whereinQ₂ is of the form —Z₁—Q₂—Z₁′— where Z₁, Z₁′ are bridging radicals, whichcan be the same or different.
 4. The polymer of claim 1 wherein Q₄ is ofthe form —Z₂—Q₄—Z₂′— where Z₂, Z₂′ are bridging radicals, which can bethe same or different.
 5. The polymer of claim 1 wherein Q₄ is a radicalof the form —CHR₁CR₀R₁′— wherein R₀ is an aliphatic polyether derivativeof the formula —[(CR₂R₂)_(x)O]_(y)—R₃ where: R₁, R₁′ is —H, C₁₋₄ alkyl;R₂, R₂′ is —H or —CH₃; x≧2; y≧2; and R₃ is a terminal group selectedfrom the group consisting of —CH₃, —H, —C₂H₅, and —NH₂.
 6. The polymerof claim 1 wherein Q₃ is


7. The polymer of claim 1 wherein Q₃ is a radical of the form—CHR₁CR₀R₁′— wherein R₀=a pendant group of the form Z₃—R₁₀—W, where Z₃is a radical bonding the R₁₀ group to the polymer; R₁ and R₁′ are —H orC₁₋₄ alkyl group; R₁₀=any linear or branched, aliphatic or aromatichydrocarbon of 2 or more carbons; and W=—N+R₁₁, R₁₂, R₁₃ where R₁₁, R₁₂,R₁₃ is a C₁₋₄ alkyl group.
 8. The polymer of claim 7 wherein Z₁ isselected from the group consisting of aryl, —CH₂—, —COO—, —CONH—, —O—,—S—, and —OSO₂O—.
 9. The polymer of claim 7 wherein R₁₀ is —(CH₂CH₂)— or—C(CH₃)₂CH₂CH₂—.
 10. The polymer of claim 1 wherein “c” is
 0. 11. Thepolymer of claim 1 wherein “d” is
 0. 12. The polymer of claim 1 whereinthe pendant group on Q₁ capable of forming hydrogen bonds is —CONH₂. 13.The polymer of claim 1 wherein the pendant group on Q₁ capable offorming covalent bonds is —CONHCHOHCHO.
 14. The polymer of claim 1wherein Q₁ has —CONH₂ and —CONHCHOHCHO pendant groups.
 15. A syntheticpolymer having hydrogen bonding capability and containing one or morepolysiloxane moieties, said polymer having the following structure:

where: w≧1; R₁, R₁′, R₂, R₃=H or C₁₋₄ alkyl; a, b>0; c, d≧0 such thatc+d>0; R₀=a group capable of forming hydrogen or covalent bonds withcellulose; Q₄=a monomer unit or a block or graft copolymer containing ahydrophilic moiety; A₁=—H, —COOH; R₄=a Z₁—R₆ radical, where: Z₁=anyradical capable of bonding the R₆ group to the polymer; R₆=a block orgraft copolymer containing siloxane bonds; R₅=Z₃—R₁₀—W, where: Z₃=anyradical capable of bonding the R₁₀ group to the polymer; R₁₀=any linearor branched, aliphatic or aromatic hydrocarbon of 2 or more carbons; andw=—N⁺R₁₁, R₁₂, R₁₃, where R₁₁, R₁₂, R₁₃ are C₁₋₄ alkyl groups.
 16. Thepolymer of claim 15 wherein R₀ is selected from the group consisting of—CONH₂, —COOH, —COO⁻M⁺, —OH, —CONHCHOHCHO, and mixtures thereof, whereinM⁺ is a counter ion.
 17. The polymer of claim 15 wherein Q₄ is of theform —Z₂—Q₄—Z₂′— where Z₂, Z₂′ are bridging radicals, which can be thesame or different.
 18. The polymer of claim 15 wherein Z₁ is selectedfrom the group consisting of aryl, —CH₂—, —COO—, —OOC—, —CONR′—,—NR′CO—, —O—, —S—, —OSO₂O—, —CONHCO—, —CONHCHOHCOHO—, —CONHCHOHCOHNH—,and where R′ is H or C₁₋₄ alkyl.
 19. The polymer of claim 15 wherein Z₁is selected from the group consisting of aryl, —CH₂—, —COO—, —CONH—,—O—, —S—, and —OSO₂O—.
 20. The polymer of claim 15 wherein R₁₀ is—(CH₂CH₂)— or —C(CH₃)₂CH₂CH₂—.
 21. The polymer of claim 15 wherein A₁ is—H and R₀ is —CONH₂.
 22. The polymer of claim 15 wherein A₁ is —H and R₀is —CONHCHOHCHO.
 23. The polymer of claim 15 wherein R₀ consists of both—CONH₂ and —CONHCHOHCHO groups.
 24. A synthetic polymer having hydrogenbonding capability and containing one or more polysiloxane moieties,said polymer having the following structure:

where: w≧1; R₁, R₁′, R₂, R₃=H or C₁₋₄ alkyl; a, b>0; c, d≧0 such thatc+d>0; R₀=a group capable of forming hydrogen or covalent bonds withcellulose; Q₄=a monomer unit or a block or graft copolymer containing ahydrophilic moiety; A₁=—H, —COOH; R₄=a Z₁—R₆ radical, where: Z₁=anyradical capable of bonding the R₆ group to the polymer; R₆=a block orgraft copolymer containing siloxane bonds;
 25. A paper sheet comprisinga synthetic polymer having hydrogen bonding capability and containingone or more polysiloxane moieties, said polymer having the followingstructure:

where: a, b>0; c, d ≧0; w≧1; Q₁=a monomer unit or a block or graftcopolymer containing a pendant group capable of forming hydrogen orcovalent bonds with cellulose; Q₂=a block or graft copolymer containingsiloxane bonds; Q₃=a monomer unit or a block or graft copolymercontaining a charge functionality; and Q₄=a monomer unit or a block orgraft copolymer containing a hydrophilic moiety, which is desirable formaking the material into a form suitable for papermaking.
 26. The papersheet of claim 25 wherein the pendant group on Q₁ capable of forminghydrogen or covalent bonds is selected from the group consisting of—CONH₂, —COOH, —COO⁻M⁺, —OH, —CONHCHOHCHO and mixtures thereof, whereinM⁺ is a counter ion.
 27. The paper sheet of claim 25 wherein Q₂ is ofthe form —Z₁—Q₂—Z₁′— where Z₁, Z₁′ are bridging radicals, which can bethe same or different.
 28. The paper sheet of claim 25 wherein Q₄ is ofthe form —Z₂—Q₄—Z₂′— where Z₂, Z₂′ are bridging radicals, which can bethe same or different.
 29. The paper sheet of claim 25 wherein Q₄ is aradical of the form —CHR₁CR₀R₁′— wherein R₀ is an aliphatic polyetherderivative of the formula —[(CR₂R₂)_(x)O]_(y)—R₃ where: R₁, R₁′ is —H,C₁₋₄ alkyl; R₂, R₂′ is —H or —CH₃; x≧2; y≧2; and R₃ is a terminal groupselected from the group consisting of —CH₃, —H, —C₂H₅, and —NH₂.
 30. Thepaper sheet of claim 25 wherein Q₃ is


31. The paper sheet of claim 25 wherein Q₃ is a radical of the form—CHR₁CR₀R₁′— wherein R₀=a pendant group of the form Z₁—R₁₀—W where Z₁ isa radical capable of bonding the R₁₀ group to the polymer; R₁ and R₁′are —H or a C₁₋₄ alkyl group; R₁₀=any linear or branched, aliphatic oraromatic hydrocarbon of 2 or more carbons; and W=—N+R₁₁, R₁₂, R₁₃ whereR₁₁, R₁₂, R₁₃ is a C₁₋₄ alkyl group.
 32. The paper sheet of claim 31wherein Z₁ is selected from the group consisting of aryl, —CH₂—, —COO—,—OOC—, —CONH—, —O—, —S—, —NHCO— and —OSO₂O—.
 33. The paper sheet ofclaim 31 wherein R₁₀ is —(CH₂CH₂)— or —C(CH₃)₂CH₂CH₂—.
 34. The papersheet of claim 25 wherein “c” is
 0. 35. The paper sheet of claim 25wherein “d” is
 0. 36. The paper sheet of claim 25 wherein the pendantgroup on Q₁ capable of forming hydrogen bonds is —CONH₂.
 37. The papersheet of claim 25 wherein the pendant group on Q₁ capable of formingcovalent bonds is —CONHCHOHCHO.
 38. The paper sheet of claim 25 whereinQ₁ has —CONH₂ and —CONHCHOHCHO pendant groups.
 39. A paper sheetcomprising a synthetic polymer having hydrogen bonding capability andcontaining one or more polysiloxane moieties, said polymer having thefollowing structure:

where: w≧1; R₁, R₁′, R₂, R₃=H or C₁₋₄ alkyl; a, b>0; c, d≧0; R₀=a groupcapable of forming hydrogen or covalent bonds with cellulose; Q₄=amonomer unit or a block or graft copolymer containing a hydrophilicmoiety; A₁=—H, —COOH; R₄=a Z₁—R₆ radical, where: Z₁=any radical capableof bonding the R₆ group to the polymer; R₆=a block or graft copolymercontaining siloxane bonds; R₅=Z₃—R₁₀—W, where: Z₃=any radical capable ofbonding the R₁₀ group to the polymer; R₁₀=any linear or branched,aliphatic or aromatic hydrocarbon of 2 or more carbons; and W=—N⁺R₁₁,R₁₂, R₁₃, where R₁₁, R₁₂, R₁₃ are C₁₋₄ alkyl groups.
 40. The paper sheetof claim 39 wherein R₀ is selected from the group consisting of —CONH₂,—COOH, —COO⁻M⁺, —OH, —CONHCHOHCHO, and mixtures thereof, wherein M⁺ is acounter ion.
 41. The paper sheet of claim 39 wherein Q₄ is of the form—Z₂—Q₄—Z₂′— where Z₂, Z₂′ are bridging radicals, which can be the sameor different.
 42. The paper sheet of claim 39 wherein Z₁ is selectedfrom the group consisting of aryl, —CH₂—, —COO—, —OOC—, —CONR′—,—NR′OC—, —O—, —S—, —OSO₂O—, —CONHCO—, and —CONHCHOHCHOHO—,—CONHCHOHCHOHNH— and where R′ is H or C₁₋₄ alkyl.
 43. The paper sheet ofclaim 39 wherein Z₁ is selected from the group consisting of aryl,—CH₂—, —COO—, —CONH—, —O—, —S—, and —OSO₂O—.
 44. The paper sheet ofclaim 39 wherein R₁₀ is —(CH₂CH₂)— or —C(CH₃)₂CH₂CH₂—.
 45. The papersheet of claim 39 wherein A₁ is —H and R₀ is —CONH₂.
 46. The paper sheetof claim 39 wherein A₁ is —H and R₀ is —CONHCHOHCHO.
 47. The paper sheetof claim 39 wherein R₀ consists of both —CONH₂ and —CONHCHOHCHO groups.48. A paper sheet comprising a synthetic polymer having hydrogen bondingcapability and containing one or more polysiloxane moieties, saidpolymer having the following structure:

where: w≧1; R₁, R₁′, R₂, R₃=H or C₁₋₄ alkyl; a, b>0; c, d ≧0 such thatc+d>0; R₀=a group capable of forming hydrogen or covalent bonds withcellulose; Q₄=a monomer unit or a block or graft copolymer containing ahydrophilic moiety; A₁=—H, —COOH; R₄=a Z₁—R₆, where: Z₁=any radicalcapable of bonding the R₆ group to the polymer; R₆=a block or graftcopolymer containing siloxane bonds;
 49. A method of making a papersheet comprising the steps of: (a) forming an aqueous suspension ofpapermaking fibers; (b) depositing the aqueous suspension of papermakingfibers onto a forming fabric to form a web; and (c) dewatering anddrying the web to form a paper sheet, wherein a synthetic polymer isadded to the aqueous suspension of fibers and/or the web, said polymerhaving the following structure:

where: a, b>0; c, d≧0; w≧1; Q₁=a monomer unit or a block or graftcopolymer containing a pendant group capable of forming hydrogen orcovalent bonds with cellulose; Q₂=a block or graft copolymer containingsiloxane bonds; Q₃=a monomer unit or a block or graft copolymercontaining a charge functionality; and Q₄=a monomer unit or a block orgraft copolymer containing a hydrophilic moiety, which is desirable formaking the material into a form suitable for papermaking.
 50. The methodof claim 49 wherein the pendant group on Q₁ capable of forming hydrogenor covalent bonds is selected from the group consisting of —CONH₂,—COOH, —COO⁻M⁺, —OH, —CONHCHOHCHO and mixtures thereof, wherein M⁺ is acounter ion.
 51. The method of claim 49 wherein Q₂ is of the form—Z₁—Q₂—Z₁′— where Z₁, Z₁′ are bridging radicals, which can be the sameor different.
 52. The method of claim 49 wherein Q₄ is of the form—Z₂—Q₄—Z₂′— where Z₂, Z₂′ are bridging radicals, which can be the sameor different.
 53. The method of claim 49 wherein Q₄ is a radical of theform —CHR₁CR₀R₁′— wherein R₀ is an aliphatic polyether derivative of theformula —[(CR₂R₂)_(x)O]_(y)—R₃ where: R₁, R₁′ is —H, C₁₋₄ alkyl; R₂, R₂′is —H or —CH₃; x≧2; y≧2; and R₃ is a terminal group selected from thegroup consisting of —CH₃, —H, —C₂H₅, and —NH₂.
 54. The method of claim49 wherein Q₃ is


55. The method of claim 49 wherein Q₃ is a radical of the form—CHR₁CR₀R₁′— wherein R₀=a pendant group of the form Z₁—R₁₀—W, where Z₁is a radical capable of bonding the R₁₀ group to the polymer; R₁ and R₁′are —H or a C₁₋₄ alkyl group; R₁₀=any linear or branched, aliphatic oraromatic hydrocarbon of 2 or more carbons; and p1 W=—N+R₁₁, R₁₂, R₁₃where R₁₁, R₁₂, R₁₃ is a C₁₋₄ alkyl group.
 56. The method of claim 55wherein Z₁ is selected from the group consisting of aryl, —CH₂—, —COO—,—CONH—, —O—, —S—, and —OSO₂O—.
 57. The method of claim 55 wherein R₁₀ is—(CH₂CH₂)— or —C(CH₃)₂CH₂CH₂—.
 58. The method of claim 49 wherein “c” is0.
 59. The method of claim 49 wherein “d” is
 0. 60. The method of claim49 wherein the pendant group on Q₁ capable of forming hydrogen bonds is—CONH₂.
 61. The method of claim 49 wherein the pendant group on Q₁capable of forming covalent bonds is —CONHCHOHCHO.
 62. The method ofclaim 49 wherein Q₁ has —CONH₂ and —CONHCHOHCHO pendant groups.
 63. Amethod of making a paper sheet comprising the steps of: (a) forming anaqueous suspension of papermaking fibers; (b) depositing the aqueoussuspension of papermaking fibers onto a forming fabric to form a web;and (c) dewatering and drying the web to form a paper sheet, wherein asynthetic polymer is added to the aqueous suspension of fibers and/orthe web, said polymer having the following structure:

where: w≧1; R₁, R₁′, R₂, R₃=H or C₁₋₄ alkyl; a, b>0; c, d≧0; R₀=a groupcapable of forming hydrogen or covalent bonds with cellulose; Q₄=amonomer unit or a block or graft copolymer containing a hydrophilicmoiety; A₁=—H, —COOH; R₄=a Z₁—R₆ radical, where: Z₁=any radical capableof bonding the R₆ group to the polymer; R₆=a block or graft copolymercontaining siloxane bonds; R₅=Z₃—R₁₀—W, where: Z₃=any radical capable ofbonding the R₁₀ group to the polymer; R₁₀=any linear or branched,aliphatic or aromatic hydrocarbon of 2 or more carbons; and W=—N⁺R₁₁,R₁₂, R₁₃, where R₁₁, R₁₂, R₁₃ are C₁₋₄ alkyl groups.
 64. The method ofclaim 63 wherein R₀ is selected from the group consisting of —CONH₂,—COOH, —COO⁻M⁺, —OH, —CONHCHOHCHO, and mixtures thereof, wherein M⁺ is acounter ion.
 65. The method of claim 63 wherein Q₄ is of the form—Z₂—Q₄—Z₂′— where Z₂, Z₂′ are bridging radicals, which can be the sameor different.
 66. The method of claim 63 wherein Z₁ is selected from thegroup consisting of aryl, —CH₂—, —COO—, —OOC—, —CONR′—, —NR′CO—, —O—,—S—, —OSO₂O—, —CONHCO—, and —CONHCHOHCOHO—, CONHCHOHCOHNH—, and where R′is H or C₁₋₄ alkyl.
 67. The method of claim 63 wherein Z₁ is selectedfrom the group consisting of aryl, —CH₂—, —COO—, —CONH—, —O—, —S—, and—OSO₂O—. [Seems redundant on 66]
 68. The method of claim 63 wherein R₁₀is —(CH₂CH₂)— or —C(CH₃)₂CH₂CH₂—.
 69. The method of claim 63 wherein A₁is —H and R₀ is —CONH₂.
 70. The method of claim 63 wherein A₁ is —H andR₀ is —CONHCHOHCHO.
 71. The method of claim 63 wherein R₉ consists ofboth —CONH₂ and —CONHCHOHCHO groups.
 72. A method of making a papersheet comprising the steps of: (a) forming an aqueous suspension ofpapermaking fibers; (b) depositing the aqueous suspension of papermakingfibers onto a forming fabric to form a web; and (c) dewatering anddrying the web to form a paper sheet, wherein a synthetic polymer isadded to the aqueous suspension of fibers and/or the web, said polymerhaving the following structure:

where: w≧1; R₁, R₁′, R₂, R₃=H or C₁₋₄ alkyl; a, b>0; c, d≧0 such thatc+d>0; R₀=a group capable of forming hydrogen or covalent bonds withcellulose; Q₄=a monomer unit or a block or graft copolymer containing ahydrophilic moiety; A₁=—H, —COOH; R₄=a Z₁—R₆, where: Z₁=any radicalcapable of bonding the R₆ group to the polymer; R₆=a block or graftcopolymer containing siloxane bonds.